You can use webmaster mode and find the tables that contain the products and try adding borders, but it might be easier to use CSS to put a div around the images. The following may get you started - you probably will need to refine it.
Add this to skin1.css:
Code:
.my_thumbnail {border: #00688B 2px solid; padding: 1px; margin: 2px;}
Then, where ever you want the border, add the div tags around it:
<div class="my_thumbnail"> </div>
For example - if you want, you could modify the product_thumbnail.tpl something like this:
Code:
{* $Id: product_thumbnail.tpl,v 1.19.2.1 2007/07/09 05:00:35 svowl Exp $ *}
{if $config.Appearance.show_thumbnails eq "Y" or ($type ne "T" and $type ne "")}
<div class="my_thumbnail"><img{if $id ne ''} id="{$id}"{/if} src="{if $tmbn_url}{$tmbn_url}{else}{if $full_url}{$http_location}{else}{$xcart_web_dir}{/if}/image.php?type={$type|default:"T"}&id={$productid}{/if}"{if $image_x ne 0} width="{$image_x}"{/if}{if $image_y ne 0} height="{$image_y}"{/if} alt="{$product|escape}" /></div>{/if}